Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/36—Amides or imides
  • C08F222/40—Imides, e.g. cyclic imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Definitions

• the present invention relates to a maleimide copolymer excellent in heat resistance, transparency, mechanical strength and processability, and a resin composition thereof.
• modified polyphenylene ether resins have been used to meet the above-mentioned requirements, and so-called heat-resistant ABS resins having improved heat resistance of ABS resins have been developed and used.
• heat-resistant ABS resin has been improved in various ways, and is superior in formability, weather resistance, and price compared to other engineering plastics. It has been used as In order to improve the heat resistance of the AS resin component in the ABS resin, an acrylic polymer obtained by polymerizing acrylonitrile and styrene together with ⁇ -methylstyrene is obtained.
• Rilonitrile-styrene-one-methylstyrene-terpolymer or acrylonitrile-butylene-styrene- ⁇ -methylinostyrene- ⁇ -vinylmale A so-called graph blend method, in which a quaternary copolymer and a rubber-reinforced resin are blended to form a resin composition, is generally employed. In these cases, the inclusion of ⁇ -methylstyrene contributes to the improvement of heat resistance, so that if the content is small, sufficient heat resistance cannot be obtained, and if it is large, the polymerization rate is slow.
• the maleimide copolymer has high heat resistance, it has the drawback that molding processability is inferior due to its low flowability when melted compared to conventional AS resins. .
• Plasticizers, lubricants, etc. are generally added to improve molding processability.However, it is necessary to keep the state of dispersion of these additives in the resin constant.
• problems such as the fact that additives appear on the surface of the molded article to improve the appearance of the molded article and to lower the heat resistance, which is the original purpose.
• Resins used in the field of vehicle exterior parts, such as automotive lamp housing, are required to be thermoplastic resins that are excellent not only in impact resistance but also in heat resistance and weather resistance.
• ABS resin is a typical example of a shock-resistant thermoplastic resin.
• ABS resin uses polybutadiene, which is a conjugated rubber, as a rubber component, and is poor in weather resistance because it is easily decomposed by ultraviolet rays.
• AAS resin containing acrylate rubber as a rubber component is used, but AAS resin is inferior to ABS resin in impact resistance.
• the inferior amount of conjugated gen-based rubber and the superior amount of ac A special AAS resin using a rubber compounded with a lylic acid ester rubber has been proposed.
• thermoplastic resin having excellent heat resistance and weather resistance
• a maleimide-based copolymer with a special AAS resin.
• thermoplastic resin composition containing the maleimide copolymer and the special AAS resin has both heat resistance and weather resistance, the surface appearance of the molded product is not deteriorated. Has the problem that In other words, there is a problem that the surface of the molded product becomes cloudy, or a part of the surface becomes opaque, and so-called poor appearance occurs. are doing.
• the present inventors have developed heat resistance. As a result of intensive studies on a maleimide-based copolymer excellent in moldability and its resin composition, the present invention was completed.
• the gist of the present invention is that the monomer unit of the maleimide monomer (a-1) is 10 to 65% by weight, preferably 15 to 65% by weight, and the aromatic vinyl unit is Monomer unit (a —
• the content of the residual maleimide monomer in the copolymer is 0.1% by weight or less, and the total volatile content other than the monomeric monomer is 0.5% by weight. Below.
• the maleimide-based monomers used in the present invention include maleimide, N—methylamineimide, N—ethylenoleimide, and N—propyl Luma Reimed, N — Isopropyl Lima Reed, N — Cyclic Hex Norem Reimed, N — Féné Norem Reimed, N — Toclay Noremare Imid, N—Normal Reimed, N—Naphthylimed, N—t—Butylmaled, N—Normal Remido, N-Release Memories, and N-Release Bromide Reimide.
• N Cyclohexylimide
• N Ontology
• N Ontology
• N Phenomena Ray Mid
• These maleimide monomers can be used alone or in combination of two or more.
• the content of the monomeric monomer unit (a-1) in the monomeric copolymer of the present invention is from 10 to 65% by weight, preferably from 15 to 65% by weight. Or from 10 to 50% by weight, more preferably from 20 to 50% by weight.
• the content of the monomer unit is less than 10% by weight, the original heat resistance is low, and when the content exceeds 65% by weight, the fluidity is poor. It is not preferable because a molded article cannot be obtained, and it also becomes a brittle resin and causes problems such as cracking when the molded article is detached from the mold.
• the aromatic vinyl monomer used in the present invention includes: Styrene, ⁇ — Methynorestyrene, ⁇ ,. Lamethinostyrene, t-butylinostyrene, chloronostyrene, bromomostylene-vinyltoluene, etc., with styrene being preferred .
• These aromatic vinyl monomers can be used alone or in combination of two or more.
• the content of the aromatic vinyl monomer unit (a-2) in the maleimide copolymer of the present invention is from 35 to 85% by weight, preferably from 40 to 70% by weight. Range.
• the content of the aromatic vinyl-based monomer unit is less than 15% by weight, the obtained maleimide-based copolymer has low flowability and poor moldability, and is 85% by weight. %, The heat resistance is low, which is not preferable.
• a cyanated vinyl monomer or an acrylate monomer may be used.
• examples of the cyanated vinyl monomer include acrylonitrile, methacrylonitrile, and fumaronitrile. Two torrs are preferred.
• examples of the acrylate monomers include methyl acrylate, ethyl acrylate, propynole acrylate, butynole acrylate, and acrylic acid acrylate. Such as black crochet.
• Methacrylate monomers include methyl methacrylate, ethyl methacrylate, propynole methacrylate, butyl methacrylate, and butyl methacrylate.
• Task Metabolic acid salts such as pheninole phthalate, isobornyl methacrylate, benzyl methacrylate, and tricyclomethyl methacrylate.
• Methyl acid is the preferred one.
• unsaturated dicarboxylic anhydride-based monomers include maleic anhydride, metaconic anhydride, and citraconic anhydride, and maleic anhydride. Anhydrides are preferred.
• examples of the vinyl carboxylic acid-based monomer include acrylic acid and methacrylic acid, and methacrylic acid is preferred. These other vinyl monomers can be used alone or in combination of two or more.
• the content of the other vinyl monomer unit (a-3) in the maleimide copolymer of the present invention is 0 to 35% by weight, preferably 0 to 25% by weight or It is 10 to 35% by weight. If the amount of the other vinyl monomer unit exceeds 35% by weight, the heat resistance, transparency, impact resistance, processability, and the like of the obtained maleimide copolymer will be impaired.
• the content of the residual maleimide-based monomer in the copolymer is 0.1% by weight or less, preferably 0.0% by weight. It is 5% by weight or less, and the total volatile components other than the maleimide monomer is 0.5% by weight or less, preferably 0.4% by weight or less.
• the content of the residual maleimide-based monomer exceeds 0.1% by weight, not only the coloration of the copolymer is remarkable and the transparency is poor, but also the thermal coloring during processing and the bleeding-out of the copolymer. It is not preferable because it is easy to cause problems.
• the total amount of the copolymer other than the maleimide monomer is Volatile components include monomers of constituent components, organic solvents and, if desired, residues of polymerization initiators and chain transfer agents. The total amount of these components is 0.5% by weight. If the ratio exceeds the above, the heat resistance of the copolymer is impaired, and problems such as the generation of silver leakage during molding are not preferred.
• the weight average molecular weight of the maleimide copolymer of the present invention measured by gel permeation chromatography (GPC) is in the range of 200 to 100,000. Obtained from at least one monomer selected from the group consisting of maleimide monomers, aromatic vinyl monomers and other vinyl monomers It contains the compound in the range of 2 to 10% by weight, preferably 3 to 9% by weight.
• the content of the compound can be determined from the ratio of the peak area to the total peak area within the corresponding range from the GPC elution curve.
• the monomer component constituting the compound can be determined by element analysis after drying the eluate of the compound component separated and collected by GPC to remove the solvent.
• the structural unit of the compound at least one kind selected from the group consisting of maleimide monomers, aromatic vinyl monomers and other vinyl monomers is used. It is a unit of a monomer, and particularly preferably contains a maleimide-based monomer unit.
• the compound must have a molecular weight of not less than 200, and a compound component of less than 200 is preferable because it causes a silver strike at the time of molding.
• a compound component having a molecular weight of more than 1000 does not contribute to the improvement of fluidity and is not useful for the purpose of the present invention. I don't like it because it doesn't work.
• the copolymer When the content of the compound is less than 2% by weight, the copolymer has low fluidity at the time of melting and is inferior in moldability, and thus is not preferable. If the content is more than 10% by weight, the heat resistance and the mechanical strength of the copolymer are lowered, and the coloring at the time of heating is liable to occur.
• the yellow index (yellowness, YI) of the maleimide copolymer of the present invention is 30 or less, preferably 25 or less.
• This YI was measured on a molded plate obtained from the copolymer, and was determined as a residual maleimide monomer and other vinyl monomers in the copolymer.
• a cyanated vinyl monomer When a cyanated vinyl monomer is used, it is closely related to the residual amount and the content of the cyanated vinyl monomer unit incorporated in the polymer in the copolymer. Relationship.
• YI is also affected when an excessive amount of a compound component is contained. In this case, it is not preferable that the strength of YI exceeds 30 because heat coloring during processing causes thermal coloring and impairs the appearance of the molded article.
• the intrinsic viscosity of the maleimide copolymer of the present invention is in the range of 0.3 to 1.5 dl Zg, preferably in the range of 0.5 to 1.2 dl Zg.
• the intrinsic viscosity is determined by dissolving the maleimide-based copolymer in N, N-dimethylformamide and using a Weberode viscometer at 25 ° C.
• a maleimide copolymer having an intrinsic viscosity of less than 0.3 d1 / g has poor practical mechanical strength and is difficult to withstand actual use, and exceeds 1.5 dl Zg. In the case of a maleimide copolymer having an intrinsic viscosity that can be obtained, the fluidity during melting is poor and the moldability is poor.
• the amount of the residual monomeric monomer, the amount of the total volatile components other than the monomeric monomer, and the weight average measured by GPC are as described above.
• a method for producing the maleimide copolymer (A) of the present invention a generally known method can be employed.
• a polymerization initiator, a chain transfer agent, a heat stabilizer and the like can be added as required.
• the polymerization initiator that can be used as desired in producing the copolymer of the present invention include generally known organic peroxides and azo compounds.
• Organic peroxides include ketone bark oxides, peroxy ketones, hydroperoxides, and ginol kilnos. One-year-olds, diasyl peroxysides, bar oxesters, bar oxycarbonates, etc.
• methyl tilketone peroxyside methyl isobutyl butyl ketone peroxyde, methyl Chinolecyclohexanone oxide, acetinoleacetone peroxide, 1,1-dibutylino ,.
• 1,1'-azobis cyclohexane-one-force olebonitrine
• 2,2'-azobis 2,2'-azobis (2-methylbutyronitrile)
• 2,2'-azobisibutyronitrinole 2,2'-azobis [2— (2_ (imidazoline-1-2-inole) propane] dihydrochloride
• 2, 2' Zobis (2-Hydroxime Chilled Mouth Piotril).
• chain transfer agent that can be used as desired in producing the copolymer of the present invention
• known chain transfer agents can be used, and melcabutane terpene oils, ⁇ -medium Chill styrene dimer and the like.
• additives such as heat stabilizers that can be used as desired in the production of the copolymer of the present invention, generally known additives can be used. Those that cause harm, such as inhibition or coloring, are not preferred.
• the rubbery graphite polymer ( ⁇ ) of the present invention is a rubbery polymer. It is obtained by subjecting a vinyl monomer to graph-polymerization in the presence of a linear polymer.
• the rubbery polymer examples include gen-based rubber, acryl-based rubber, EPDM rubber, chlorinated polyethylene rubber, silicone rubber, and silicone-acrylic rubber. Elastomers such as composite rubber can be used. From the viewpoint of impact resistance, gen-based rubber, particularly buta- gen-based rubber, is preferred.
• the butadiene rubber include polybutadiene rubber, butadiene-styrene copolymer rubber, butadiene-vinyltoluene copolymer rubber, and butadiene rubber.
• Polyacrylonitrile copolymer rubber butadiene methacrylonitrile copolymer rubber, butadiene methyl acrylate copolymer rubber, butadiene monoacrylate 2-Ethyl hexyl copolymer rubber, butadiene-methyl methacrylate copolymer rubber, butadiene-methyl methacrylate copolymer rubber, etc. No. It also contains a terpolymer rubber composed of 50% by weight or more of 1,3-butadiene units and has a glass transition temperature of 0 ° C or less.
• the vinyl monomer used is a small amount selected from the group consisting of aromatic vinyl monomers, acrylate monomers and derivatives thereof, and cyanated vinyl monomers. It is at least one type of vinyl monomer.
• Aromatic vinyl monomers that can be used in the present invention include alkylstyrenes such as styrene, polymethyltin styrene, t-butylstyrene, and the like; and chlorostyrene-bromostyrene and the like.
• alkylstyrenes such as styrene, polymethyltin styrene, t-butylstyrene, and the like; and chlorostyrene-bromostyrene and the like.
• NOLOGENIDAI styrene vinyl torenene and the like, which may be used alone or as a mixture of two or more. It is preferable to use styrene or one methylstyrene alone or as a mixture of two types.
• the (meth) acrylate monomers and derivatives thereof that can be used in the present invention include methyl acrylate, methyl methacrylate, and ethacrylonitrile.
• Methyl acetic acid, ethynole acrylate, ethynole methacrylate, ethyl ethacrylate acrylate These include butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and derivatives thereof. These can be used alone or in combination of two or more.
• Preferred are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, and the like.
• the cyanated vinyl monomers that can be used in the present invention include acrylonitrile resin, halogenated acrylonitrile resin, and metaacrylonitrile. Nore, Etacrilonitril Fumaronitrile and the like and derivatives thereof, which can be used alone or in combination of two or more. Preference is given to acrylonitrile and no or metaacrylonitrile.
• other vinyl monomers such as maleimide, N-methylmaleimide, N-vinylinoleimide, etc. Imide-based monomers and derivatives thereof, acrylamides and derivatives thereof, and the like can be used.
• the present invention also provides an aromatic vinyl monomer and a (meth) acrylic ester in the presence of the above-mentioned maleimide copolymer (A) and a rubbery polymer.
• Rubbery polymer obtained by polymerizing at least one vinyl monomer selected from the group consisting of vinyl monomers, derivatives thereof, and cyanated vinyl monomers
• the present invention also relates to a maleimide resin composition containing a copolymer (B).
• the component (B) also has a role of a rubber-reinforced resin component for expressing the impact resistance of the resin composition.
• composition ratio of the maleimide copolymer (A) and the rubbery graphite copolymer (B) in the maleimide resin composition is as follows: (8) 5 to 95 wt. (8) 5 to 95% by weight, preferably 5 to 60% by weight, relative to 40 to 95% by weight. However, the total amount of (A) and (B) is 100% by weight.
• the composition ratio of the rubbery polymer and the vinyl monomer is 5 to 8 for the rubbery polymer.
• the total amount of the rubber polymer and the vinyl monomer is 100% by weight. If the amount of the rubber-like polymer is less than 5% by weight, the impact resistance is insufficient, and if it exceeds 80% by weight, the hardness of the resin is insufficient, which is not preferable.
• the rubber-like polymer such as butadiene rubber used in the present invention preferably has a number average particle diameter in the range of 0.15 to 0.4 / m, more preferably 0.2 to 0.4 / m.
• the range is 0.35 zm.
• the intrinsic viscosity of the non-graphite polymer contained in the rubbery graphite copolymer (B) having poor impact resistance is preferably in the range of 0.4 to 1.2 dl Zg, and more preferably.
• the range is 0.5 to 0.5 SdlZg.
• the impact resistance of the maleimide resin composition is inferior.
• the intrinsic viscosity of the coalesce exceeds 1.2 dl Zg, the flowability of the maleimide resin composition is low and the molding processability is poor.
• the graphite fraction of the rubbery graphite copolymer (B) is from 20 to 80%, preferably from 20 to 60%, more preferably from 25 to 50%. It is in the range of ⁇ 50%, more preferably in the range of 30-45%. If the graphitic ratio of the graphitic copolymer is less than 20%, the graphitic copolymer is likely to agglomerate, thereby deteriorating the appearance of the maleimide resin composition. . On the other hand, when the graphitization ratio of the graphite copolymer exceeds 80%, the impact resistance of the maleimide resin composition becomes inferior.
• the rubbery graphitic copolymer (B) is prepared by reacting acrylonitrile (b-2) and styrene (b-2) in the presence of butadiene rubber (b-1).
• b — 3) is obtained by graph polymerization ( ⁇ ,).
• the content of the butadiene rubber (b_l) in the rubbery graphite copolymer (B,) is 100% by weight of the total of the components (b-1) to (b-3). It should be in the range 35-70% by weight, preferably 40-65% by weight. If the content is less than 35% by weight, a large amount of the rubber reinforced resin must be incorporated into the resin composition in order to increase the surface impact resistance of the resin composition. For this reason, the heat resistance of the maleimide resin composition is inferior. On the other hand, when the content exceeds 70% by weight, the molded appearance of the maleimide resin composition becomes poor.
• the content of acrylonitrile and styrene in the rubber-reinforced resin (B,) was 7.5 to 29 for acrylonitrile (b-2). 25% by weight, styrene (b-3) must be in the range of 165 to 48.75% by weight, and (acrylonitrile (b _ 2) / (acrylonitrile The ratio represented by (b-2) + styrene (b-3))))) must be 0.25 to 0.45.
• the rubbery graphite copolymer (B) is prepared by a two-stage graph polymerization (Bz) as follows. That is, in the presence of 35 to 70% by weight of a butadiene rubber, 10 to 40% by weight of acrylonitrile 30 to 90% by weight of styrene and ⁇ -methylstyrene A graphene polymer obtained by polymerizing 45% by weight or less, preferably 35% by weight or less of lene,
• the number average particle diameter of the butadiene rubber of the graphite polymer is in the range of 0.15 to 0.4 zm;
• the graphitic polymer is expressed by (weight of acrylonitrile) ⁇ ((weight of acrylonitrile) + (weight of styrene)).
• a monomer mixture (d) having a weight ratio of 0.1 to 0.4 the weight ratio of (acrylonitrile) ⁇ (( ⁇ A monomer mixture having a weight ratio of 0.1 to 0.4 expressed by the weight of chlorotrilinole) + (the weight of styrene or ⁇ -the weight of methyl styrene)
• a graphitic polymer obtained by polymerizing 40 to 60 parts by weight comprising (a monomer mixture (d) and a monomer mixture (e) total 100 parts by weight)
• the intrinsic viscosity of the non-graphite polymer contained in the graphitic polymer is 0.5 to 1.3 dlZg after polymerizing the monomer mixture (d), 0.3-1.O dl Zg after polymerization of the monomer mixture (e), and the intrinsic viscosity of the polymer is lower after (e) polymerization than after (d) polymerization.
• the weight ratio is less than 40 parts by weight of the monomer mixture (d) and more than 60 parts by weight of the monomer mixture (e), the impact resistance of the final resin composition becomes inferior, which is not preferable.
• the weight ratio is more than 60 parts by weight of the monomer mixture (d) and less than 40 parts by weight of the monomer mixture (e)
• the appearance of the final resin composition tends to be poor. Not good.
• the inherent viscosity of the non-graphite polymer after polymerization of the monomer mixture (d) is from 0.6 to 1.0 OdlZg, and the viscosity of the monomer mixture (e) after polymerization is low.
• the intrinsic viscosity of the graphite polymer is 0.4 to 0.8 dl Zg.
• the impact resistance according to the present invention indicates that the intrinsic viscosity of the non-graphite polymer is less than 0.5 after polymerization of the monomer mixture (d) and less than 0.3 after polymerization of the monomer mixture (e).
• the intrinsic viscosity of the non-graphite polymer exceeds 1.3 after polymerization of the monomer mixture (d), and exceeds 1.0 after polymerization of the monomer mixture (e). If it exceeds, the moldability becomes remarkably inferior and is not preferred. If the intrinsic viscosity after polymerization of the monomer mixture (d) is lower than that of the monomer mixture (e), the resulting final resin composition is inferior in impact resistance and molding processability, which is not preferable.
• the method for producing the rubbery graphite copolymer (B) of the present invention generally known methods such as emulsion polymerization, bulk polymerization, suspension polymerization, solution polymerization, emulsion suspension polymerization, and emulsion bulk polymerization can be employed. However, emulsion polymerization is preferably used.
• thermoplastic resin (C) besides the above-mentioned maleimide copolymer (A) and rubbery graphite copolymer (B) as an optional component.
• This component (C) is a component used to improve the molding processability, appearance, and mechanical performance of the resin composition.
• the component include an acrylic resin.
• the resin composition of the present invention contains the above-mentioned maleimide copolymer (A) and rubbery graphite copolymer (B) in an amount of 5 to 95 parts by weight, preferably 40 to 100 parts by weight.
• the total of the components (A) and (B) should be 100 parts by weight in the range of up to 95 parts by weight, the latter in the range of 5 to 95 parts by weight, and preferably in the range of 5 to 60 parts by weight. It was mixed with If the amount of the rubbery graphite copolymer (B) is less than 5 parts by weight, the resulting resin composition has insufficient impact resistance, and if the amount exceeds 95 parts by weight. If the amount is too small, the heat resistance of the obtained resin composition will decrease.
• the amount of other hard thermoplastic resin (C) that can be blended as an optional component is 0 to 30 parts by weight based on the total 100 parts by weight of the above components (A) and (B). 0 parts by weight. If the proportion exceeds 300 parts by weight, improvement in heat resistance and impact resistance of the finally obtained resin composition cannot be expected.
• a hindered phenol-based antioxidant / phosphite-based stabilizer is used for the purpose of improving thermal stability, and a weather-resistance is improved.
• Tentzov unon-based UV absorbers Hindered amine-based stabilizers and benzotriazole-based UV absorbers are used for the purpose of improving processability. It is possible to mix amide-based lubricants such as amides and metal stones alone or in combination. Furthermore, a flame retardant can be blended into a flame retardant resin composition.
• the resin composition of the present invention can be used in various molding processing fields such as injection molding, extrusion molding, and vacuum molding.
• the molded product is subjected to plating, vacuum evaporation, sputtering, and the like. It is also possible to perform a bright process such as a brushing process.
• Component (A) is 5 to 95% by weight
• component (B) is 5 to 95% by weight
• the content of the other thermoplastic resin (C) is 75% by weight or less, and is determined by ((B) X (weight ratio of butadiene rubber)) Z ((A) + (B) + (C)).
• the rubber component weight fraction shown is 3 to 30% by weight.
• the rubbery graphite copolymer (B) is one type of a composite rubber of a gen-based rubbery copolymer and an acrylic acid ester-based rubbery copolymer.
• the gen-based rubbery polymer used in this case is a copolymer comprising at least 70% by weight of gen and at most 30% by weight of another monomer copolymerizable therewith. is there.
• the gen include 1,3-butadiene, isoprene, and chloroprene, and other copolymerizable monomers include acryloni.
• examples include cyanated vinyl monomers such as tolyl and aromatic vinyl monomers such as styrene.
• Preferred examples of the gen-based rubbery copolymer include polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, and styrene-butadiene copolymer.
• coal rubber is preferred, and polybutadiene rubber is most preferred.
• the number average particle size in the latex is the number average particle size in the latex
• Large particles having a size of 0.2 to 1.0 m are preferable in terms of impact resistance of the resin composition.
• Such large particles of rubber may be those obtained slowly over several stages of seed polymerization, but can be obtained efficiently by a bloating operation. That is, by adding an acid group-containing copolymer latex to a base rubber latex of 0.03 to 0.15 ⁇ m, the base rubber latex was enlarged to a desired size. Use of rubber latex is preferred.
• the acid group-containing copolymer latex is composed of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, carboxylic acid, sorbic acid and P_S
• One or more unsaturated acids selected from the group consisting of styrenesulphonic acid in an amount of 3 to 40% by weight and an alkyl acrylate ester having 1 to 12 carbon atoms. And more than 97 to 60% by weight of the compound can be obtained by emulsion polymerization.
• copolymers of methacrylic acid and butyl acrylate are mentioned as preferred examples.
• the acid group-containing copolymer latex added for the enlarging operation is 100 parts by weight of a gen-based rubbery copolymer latex (the solid content) as the base rubber. ), And 0.5 to 8 parts by weight of solid content.
• the base rubber latex should have a pH of 9 or more and have a high acid group-containing copolymer latex containing unsaturated acid. Must be used.
• the enlarged rubber has a particle size distribution of two dispersions.
• a resin composition of the present invention can be obtained with almost no problem in physical properties.
• a rubber component consisting of one kind of a composite rubber of a jen rubber and an acryl rubber, or a jen rubber and an acrylic rubber, A rubber-based polymer composed of two types, a composite rubber and an acrylic rubber, is preferred.
• the composite rubber is composed of an acrylate ester, a crosslinking agent and a graphite cross-linking agent in the presence of 5 to 40% by weight (as a solid content) of a gen-based rubber latex. It is obtained by seed polymerization of 60 to 95% by weight of the monomer mixture (100% by weight in total).
• the acrylate used here is a benzene such as an alkyl acrylate having an alkyl group of 1 to 12 carbon atoms, a phenyl group or a benzyl group.
• Acrylic acid aromatic ester having a ring Preferred examples thereof include n-butyl acrylate, 2-ethylhexyl acrylate, and ethyl acrylate.
• One or two or more species can be used.
• Functional groups such as linoleic acid, dimethylaminoethyl acrylate, etc.
• a acrylate compound can also be used in combination with the above.
• Crosslinking agents include divinylbenzene, ethylene glycol resin acrylate, ethylene glycol resin acrylate, butylene glycol acrylate, and the like. , Buty Ling Guangzhou Adventure, Polyethylene Glyco-Regular Cry Rerate, Polyethylene Glyco Reno Glyme Rental, Trial Examples of such compounds include, but are not limited to, tri-methylate, tri-methylate-sodium, trimethylol-propane, and tri-atalylate. Examples include the aryl creat, aryl memo cre- ate, and aryl umn connection. The type and amount of the cross-linking agent and the graphite cross-linking agent are determined so that the gel content of the rubber component and the ratio of the graphite component to the rubber component are in the optimum ranges.
• the ratio of the rubber (the total amount of the seeded portion and the portion present alone) is 5 to 40% by weight of the gen-based rubber and 95 to 60% by weight of the acryl-based rubber. If the proportion of the gen-based rubber is less than 5% by weight, the impact resistance of the resin composition tends to decrease, while if it exceeds 40% by weight, the weather resistance of the resin composition tends to decrease. You.
• the seed polymerization is carried out by emulsion polymerization, in which the monomer mixture is added dropwise to the polymerization system while polymerizing as needed, or the monomer mixture is impregnated in advance into the conjugated diene rubbery copolymer.
• the procedure of adding an initiator, etc., and then polymerizing, and the procedure of impregnating the monomer mixture and then polymerizing are performed while changing the composition of the monomer mixture in each stage. There is a method of performing it continuously.
• a new emulsifier can be added for the purpose of improving the stability of the polymerization system.
• the gel content (toluene-insoluble content) of the rubber component obtained by the seed polymerization is 85% by weight or more, preferably 90% by weight so as not to impair the surface appearance of the resin composition. % Or more.
• the gel content may be optimized by optimizing the type and amount of the crosslinking agent used in combination with the acrylate during the seed polymerization, or by setting the polymerization temperature, the amount of the initiator, or the polymerization time (simple amount). It can be obtained by adjusting the dropping time when dropping the monomer mixture).
• the obtained rubber component latex is continuously subjected to graphitization.
• Graph polymerization is a rubber component latex In the presence of 40 to 70% by weight (as solid content), a monomer mixture composed of a cyanated vinyl monomer and an aromatic vinyl monomer 60 to 30% by weight This is carried out by polymerizing the polymer. If the rubber component is less than 40% by weight, the amount of the graphite copolymer required for developing the impact resistance of the resin composition increases, and the amount of the maleimide-based copolymer increases accordingly. It is not preferable because the heat resistance is reduced due to reduced heat resistance. On the other hand, if it exceeds 70% by weight, it is not preferable because coarse particles are generated in the coagulation step performed after the graphitization and cannot be recovered.
• Examples of cyanated vinyl monomers used in the graph polymerization include acrylonitrile, methacrylonitrile, ethacrylonitrile, and methacrylonitrile. Examples thereof include maleonitrinole and fumaronitrile, and acrylonitrile is a preferred example.
• Examples of the aromatic vinyl monomer include styrene, ⁇ -methynolethylene, ⁇ —methinorestylene, ⁇ -methylstyrene, and 2,4-diene. Examples include methinorestyrene, p-t-butylstyrene, and halogenated styrene, and styrene or -methylstyrene is a preferred example. .
• the ratio of the cyanated vinyl monomer to the aromatic vinyl monomer used depends on the impact resistance of the resin composition, the molding processability, and the heat-resistant coloring property. O 45 to 55% by weight and aromatic vinyl compound 85 to 55% by weight o
• a known emulsion polymerization method can be used for the graphitization method. Polymerize after charging monomer mixture at once The method, the method of charging a part of the monomer mixture first and dropping in the remainder, and the method of polymerizing as needed while dropping the entire amount of the monomer mixture, are divided into one or two or more stages. In this case, the type and composition ratio of the monomer mixture in each stage can be changed. In the case of graphite polymerization, the entire monomer mixture often becomes a copolymer in a partially free form without being bonded to the rubber component as a graphite component. . Such a copolymer will be present as a copolymer (C) in the resin composition.
• the resulting graph preparative copolymer (B 3) La Te click scan is coagulated by a known method, dewatering, washing, through steps such as drying, and graph preparative copolymer (B 3) can get.
• Ma ray of interest with the case is et to the copolymer (C) to the rubber-graph preparative copolymer (B 3), used to be Ma Rei Mi de-based copolymer (A) and A mid copolymer resin composition can also be constituted.
• the copolymer (C) used in the present invention is obtained by copolymerizing a monomer mixture consisting of 15 to 45% by weight of an unsaturated cyanide compound and 85 to 55% by weight of an aromatic vinyl compound. It is obtained by doing.
• the cyanated vinyl-based monomer and aromatic vinyl-based monomer are preferably used in the same kind and amount as the compounds used in the above-mentioned graphite copolymer (B).
• Copolymer (C) is Ru if mower which is a by-product graph preparative polymerization during cormorants I described in the description of the graph preparative copolymer (B 3), a separately manufactured Ri by the object Using things It is good.
• the purpose of using the copolymer (C) is to use a copolymer having a low molecular weight to further improve the moldability of the resin composition, and to increase the melt strength during heating and melting. For example, a copolymer having a very high molecular weight may be used.
• the copolymer (C) is used as needed, and the amount used is 0 to 40% by weight.
• the production of the copolymer (C) is carried out by a known polymerization method, but preferably produced by a solution polymerization method or a suspension polymerization method.
• Ma Lei mi de copolymer resin composition of the present invention Ma Lei mi de copolymer (A) 4 0 ⁇ 8 5 parts by weight and the graph preparative copolymer polymer (B 3) 1 5 ⁇ 5 0 Parts by weight and, if necessary, 0 to 40 parts by weight of the copolymer (C) (however, the component (A),
• the total of (B a) and (C) is 100 parts by weight). If the amount of the graphite copolymer (B 3 ) is less than 15 parts by weight, the impact resistance of the resin composition will be low, while if it exceeds 50 parts by weight, the heat resistance of the resin composition will be low. Tends to decrease. If the amount of the maleimide-based copolymer (A) is less than 40 parts by weight, the heat resistance of the resin composition decreases, while if it exceeds 85 parts by weight, the resin composition becomes less. It is not preferable because impact resistance is reduced. In addition, the copolymer
• parts means “parts by weight” and “%” means “% by weight”.
• Various measurement methods were performed according to the following methods.
• composition ratio of each monomer unit of the copolymer was determined by elemental analysis.
• Yellow Index uses a 1-inch injection molding machine to produce a 3 mm thick plate specimen at a cylinder temperature of 260 ° C. It was molded and measured according to ASTM D-1925.
• the intrinsic viscosity [/?] Of the copolymer was determined by dissolving the copolymer in N, N-dimethylformamide at 25 ° C using a Ubbelode type viscometer.
• the short-cut pressure is the minimum injection pressure required to fill the required amount of resin in the mold, and includes the molding temperature, the mold, the molding machine, and the resin. Although it depends on the melt viscosity, etc., when molding under certain conditions, it can be determined that the lower the pressure, the higher the moldability of the resin.
• Spiral flow length is the length of a molded product obtained by molding with a constant injection pressure using a mold with a width of 1 cm and a thickness of 2 mm and the end released to the outside of the mold. This indicates that the larger the value, which is an index for comparing fluidity, the better the moldability of the resin.
• the values obtained by measuring the lengths of the molded products when molded at a cylinder temperature of 260 ° C. and an injection pressure of 450 k / cm 2 with a 1-ounce molding machine are shown.
• Exposure was carried out for 50,000 hours using an H-type under the conditions of a black panel temperature of 63 ° C and rain (60 minutes of cyclic rain, 12 minutes).
• the surface gloss at this time was measured by the method (10) described above, and evaluated by the gloss retention (%) with respect to the surface gloss before exposure.
• Monodispersed polystyrene was measured by GPC as a standard.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) of the maleimide copolymer and their ratio MwZMn are based on the polystyrene standard polymer from the GPC elution curve. It was calculated from the calculated Mw and Mn.
• the latex polymer is coagulated with isopropyl alcohol, the obtained polymer is extracted with acetone, centrifuged, filtered, and the filtrate is evaporated to give acetone.
• the polymer was dissolved in N, N-dimethylformulamide and measured at 25 ° C with a Ubbelode viscometer.
• the resin composition was molded into a 100 mm x 100 mm x 3 mm (thickness) specimen at 260 ° C using a 2 ounce injection molding machine, and was prepared according to ASTM D-3767. Using a Shimadzu HTM-1 type high-speed impact tester, measurements were taken at 23 ° C at a speed of 3.3 msec. However, the striker used one inch and two inches, and the support frame used three inches.
• the polymerization reaction solution was continuously withdrawn using the gear pump provided, and the polymerization reaction solution was allowed to stay in a heat exchanger maintained at 150 ° C. for about 20 minutes.
• a 2-vent type 30 mm twin-screw extruder controlled at 230 ° C, with the first vent at atmospheric pressure and the second vent at 20 torr.
• the one and Bae Les Tsu Toihi to give Bae Les Tsu City of Ma Lei mi de copolymer.
• Various physical properties of the maleimide copolymer were determined, and are shown in Table 1. Comparative Example 1
• Example 1 Using the same apparatus as in Example 1 and setting the temperature of the polymerization reactor to 95 ° C, 1,1'-azobis (cyclohexane) is used. The same procedure was followed except that 0.18 parts of t-dodecinolenecaptan was used and 0.22 parts of t-dodecinolemelkabutane, and a pellet of a maleimide copolymer was obtained. . This pellet The mold was treated and treated in the same manner as in Example 1. Table 1 shows the results.
• Example 1 Using the same apparatus as in Example 1 and Comparative Example 2, the temperature of the polymer reactor was set to 150 ° C., and 1,1′-azobis (cyclohexanone 1—canoleboni) was used. The same procedure was followed except that the trinole) was 0.001 part and the t-dodecylmenolecaptan was 0.05 part, and the pellets of the maleimide copolymer were obtained. I got it. This pellet was molded and measured in the same manner as in Example 1. Table 1 shows the results.
• Example 1 Using the same apparatus as in Example 1, 30 parts of N-vinyl maleimide, 30 parts of styrene, 40 parts of methylethylketone, and azobisisobutyronitrile 0 1 part, 0.4 parts of n-octyl mercaptan butane, the temperature in the polymerization reactor was set to 120 ° C, the average residence time was 90 minutes, and the second reaction was carried out. The same operation as in Example 1 was performed except that the barrel temperature of the twin-screw extruder was set at 270 ° C. without using a reaction apparatus, and a pellet of a maleimide copolymer was obtained. Was. This pellet was molded and measured in the same manner as in Example 1. Table 1 shows the results.
• Example 2 Using the same apparatus as in Example 2, 0.005 parts of azobisisobutylonitrinophenol and 0.3 part of n-year-old quinolone melanobutane were supplied, and the temperature in the polymerization reactor was increased. At 130 ° C A pellet of a maleimide copolymer was obtained by performing the same operation as in Example 2 except for the above. This pellet was molded and measured in the same manner as in Example 1. Table 1 shows the results.
• Example 2 Using the same apparatus as in Example 2, 0.4 parts of azobisisobutylonitrile and 1 part of n-octylmethylphenol were supplied, and the temperature in the polymerization reactor was adjusted to 100 parts. The same operation as in Example 2 was performed except that the temperature was changed to ° C to obtain a pellet of a maleimide copolymer. This pellet was molded and measured in the same manner as in Example 1. Table 1 shows the results.
• Example 1 Using the same apparatus as in Example 1, 25 parts of N-phenylmaleimide, 40 parts of styrene, 15 parts of acrylonitrile 20 parts of methylethylenoketone, 1,1'-azobis (six-mouth hexane-1 1 _ canoleponitrinole) 0.015 parts, t-dodecylmercabutane 0.03 parts are supplied to the polymerization reactor The inside temperature was set to 130 ° C, and the barrel temperature of the twin-screw extruder was set to 250 ° C, and the same operation as in Example 1 was performed to obtain a maleimide copolymer. I got a letter. This pellet was molded and measured in the same manner as in Example 1. Table 1 shows the results.
• Example 3 Using the same apparatus as in Example 1, 0.1 parts of 1,1'-azobis (cyclohexanone), 0.1 part, t The procedure of Example 3 was repeated except that 0.2 part of dodecylmercaptan was supplied and the temperature in the polymerization reactor was set to 100 ° C, and the pellets of the maleimide copolymer were obtained. I got it. This beret was molded and measured in the same manner as in Example 1. Table 1 shows the results.
• Ethylene bis stearyl amide (Kao Co., Ltd.), which is generally used as a lubricant in the above-mentioned pellets (100 parts)
• KA 0 WAXEBP One part of KA 0 WAXEBP was added and extruded at a barrel temperature of 250 ° C. with a 3 O mm twin-screw extruder to obtain a pellet.
• this pellet was measured by the same operation as in Example 1, the YI was 45, the vicat softening temperature was 14.6 ° C, and the short shot was observed.
• the heat pressure was 33 kg Z cm 2 G, and the snow and spiral flow length was 16 cm.
• the Examples and Comparative Examples show that the maleimide copolymer of the present invention has high heat resistance and excellent moldability.
• the content of the compound component having a molecular weight of 200 to 100, which is out of the range of the present invention, is small, the fluidity is inferior.
• the content of the compound component having a molecular weight of 200 to 1000 as a constituent component is large, the fluidity is high but the heat resistance is impaired, and coloring occurs upon heating. I understand.
• the maleimide-based copolymer of the present invention has improved fluidity without causing a decrease in heat resistance which occurs when a generally used lubricant or the like is added. I understand.
• Example 1 25 50 25 0.05 0.25 6 70 24 6 0.6.68 25 137 28 Akira 1 25 50 25 0.05 0.30 0.5 or less __1> 0.65 21 138 12 Comparative school 12 25 50 25 0.05 0.25 13 70 24 6 0.56 36 134 36 Example 2 62 38 0.05 0.4 9 45 55 0 46 26 184 11 Comparative Example 3 62 38 0.05 0.4 14 45 55 0.44 36 178 14 Comparative Example 4 62 38 0.05 0.4.45 45 55 0.50 25 192 6 Example 3 35 50 15 0.05 0.35 7 60 30 10 0.76 22 15) 22 Comparative Example 5 35 50 15 0.05 0.4.1 62 32 8 0.78 19 153 12 Note) PhMI: N phenyl maleimide, St: Styrene, AN: Acrylo:
• Polybutadiene latex 60 parts Pure water 140 parts Dextrose 0.6 parts Pyrrolinic acid soda 0.3 parts Ferrous sulfate 0 Then, the content of the polymerization reactor was heated to 60 ° C, and the mixture was heated to 60 ° C, and the mixture was heated to 120 ° C., and the mixture was heated to 60 ° C. 8 copies, Kumen Hydrono ,. A mixture of 0.2 part of oxide and 0.5 part of t-dodecylmenolecabutane was added continuously over 2 hours, and then aged at 60 ° C for 2 hours to complete the polymerization.
• the obtained polybutadiene rubber reinforced resin latex was coagulated with sulfuric acid, dehydrated and dried to obtain a powder of polybutadiene rubber reinforced resin B-1.
• the number average particle diameter of the polybutadiene rubber used was 0.3 ⁇ m.
• the intrinsic viscosity of the obtained unpolymerized polymer of the rubber-reinforced resin B-1 was 0.69 dl / g, and the graphitization ratio was 39.
• the mixture (A) in the ratio shown in Table 2 was supplied to a glass polymerization reactor equipped with a 5-liter stirrer. Then the polymerization reactor The temperature of the contents was raised to 60 ° C, and the amount of peroxide at the amount shown in Table 2 was added, and the mixture was polymerized until no heat was generated in the polymerization reactor. After the polymerization, the mixture was cooled to 60 ° C., and the mixture (B) having the ratio shown in Table 2 was continuously supplied. After the end of the supply, the polymerization in the reactor was stopped, and then 0.03 parts of cumene hydroperoxide was added, and polymerization was carried out at 60 ° C for 0.5 hours to complete the polymerization. I let you.
• the obtained polybutadiene rubber-reinforced rubber particles are coagulated with sulfuric acid, dehydrated and dried to obtain rubbery graphite copolymer B-2 and B-3 powders.
• the number average particle diameter of the used butadiene rubber was 0.3 ⁇ m.
• Tables 3 and 4 show the maleimide copolymers A-1 to A-3 and rubbery graphite copolymers B-1 to B_3 obtained in Examples 1 to 3, respectively.
• 100 parts of each compound were used as stabilizers as a phenolic antioxidant (Ante W-400, trade name, 0.2 parts of Kawaguchi Chemical Co., Ltd.) and 0.2 parts of phosphite-based stabilizer (ADEKA STAB C, trade name, manufactured by Asahi Denka Co., Ltd.) were added and mixed well.
• the pellet was formed at 250 ° C. with a twin screw extruder of 3 O mm 0 to obtain a pellet of a maleimide resin composition.
• Table 3 shows the performance evaluation results of the obtained resin composition.
• EBS Ethylene bistea amide (KAO WAX EBP, manufactured by Kao Corporation) Table 4 Male imide-based rubber reinforced Bica cut face bite bite Combined (A) Street fat (B) Softening temperature Strength Dex.
• Kind (part) Kind (part) (t) (kgf ⁇ mnij (g / 10 min))
• Example 5 A-1 600 B-2 4 0 1 2 0 4 7 0 0 2.4
• Comparative example 8 A-2 6 0 B-2 4 0 1 2 2 4 6 0 0.9
• Comparative example 9 A-3 6 0 B-2 4 0 1 1 2 3 0 0 0 5.7
• Example 6 A-16 0 B-3 4 0 1 2 0 4 3 0 0 2.2
• the pellet was formed at 250 ° C. using a 3 O mm 0 twin screw extruder to obtain a pellet of a maleimide resin composition.
• Table 5 shows the performance evaluation results of the obtained resin composition.
• the maleimide copolymers A_4 to A-6 obtained in Example 2 and Comparative Examples 3 to 4 and the rubbery graphite copolymer B-1 obtained in Reference Example B-1 and a conventional method The AS resin composed of 30% by weight of acrylonitrile units and 70% by weight of styrene units produced by the suspension polymerization method was used in the proportions shown in Table 2. Same as Example 4 except that the same amount of stabilizer as in Example 4 was added to 100 parts of the obtained compound and the temperature of the extruder was set at 280 ° C. By performing the above operation, a pellet of a maleimide resin composition was obtained. Table 3 shows the performance evaluation results of the obtained resin composition.
• Table 2 shows the maleimide copolymers A-7 and A-8 obtained in Example 3 and Comparative Example 5 and the rubbery graphite copolymer B-1 obtained in Reference Example B_1.
• Example 4 was repeated except that the same amount of the same stabilizer as in Example 4 was added to 100 parts of the obtained blend, and the temperature of the extruder was set to 260 ° C. By performing the same operation as described above, a pellet of a maleimide resin composition was obtained.
• Table 3 shows the performance evaluation results of the obtained resin composition.
• Maleimide copolymer A 270 parts and rubber reinforcing resin B — 130 parts
• the same amount of one stabilizer was added, and the same operation as in Example 4 was performed at an extruder temperature of 250 ° C. to obtain a pellet of a maleimide resin composition.
• Table 3 shows the performance evaluation results of the obtained resin composition.
• the composition of the obtained copolymer was 31% by weight of N-phenylmaleimide unit, 54% by weight of styrene unit, and 15% by weight of acrylonitrile unit. .
• the residual monomer content was 0.015% by weight of N-vinyl maleimide, 0.86% by weight of volatile components other than N-vinyl maleimide, and the intrinsic viscosity was At 0.75, the vicat softening temperature was 142 ° C and Y 1 was 42.
• a 5-liter glass polymerization reactor equipped with a stirrer was charged with the following components.
• Polybutadiene latex (as solid content) 45 parts Pure water 140 parts Dextrose 0.35 parts Pyrolic acid soda 0.2 parts Sulfuric acid Ferrous iron 0.06 parts Potassium rosinate 0.8 parts Acrylonitrinole 8.1 parts Styrene 19.9 parts t — Dodecinolone 0.14 parts of polybutadiene having a number average particle diameter of 029 m was used.
• a 5-liter glass polymerization reactor equipped with a stirrer was charged with the following components.
• Polybutadiene latex (as solid content) 45 parts Pure water 40 parts Dextrol 0.35 parts Sodium pyrrolate 0.2 parts Ferrous sulfate 0 0.06 parts of potassium rosinate 0.8 parts of acrylonitrile 8.1 parts of styrene 19.9 parts t-dodecinolemenolecaptan 0.14 parts of poly
• the number average particle diameter of butagen was 029 m.
• the temperature of the charge was raised to 60 ° C., and 0.084 parts of cumene hydroperoxide was added and polymerized. After the polymerization, the mixture was cooled to 60 ° C, and (B-6) was 7.9 parts of acrylic triethanol.
• the first polymerization is indicated as 1st, and the subsequent polymerization is indicated as 2nd.
• the obtained polybutadiene-reinforced resin latex has a phenolic antioxidant (Antage W-40) 0, trade name, manufactured by Kawaguchi Chemical Co., Ltd.)
• the solid was coagulated, dehydrated and dried to obtain a polybutadiene reinforced resin (B) as a white powder.
• Table 8 shows the results of the Izod impact strength, the vicat softening temperature, and the thermal decomposability (silver stroke) of Examples 10 to 13 and Comparative Example 17.
• thermoplastic resin composition Production of thermoplastic resin composition
• Adeka stub LA — 63 P manufactured by Asahi Denka Co., Ltd.
• Ethylene bis stearoamide 1 part
• Magnesium stearate 0.3 parts
• Section Silicon Oil SH200 made by Toray Industries, Inc. Silicone
• the maleimide-based copolymer and its resin composition of the present invention have excellent heat resistance and excellent moldability, and can be used in various industries such as electronics, electric equipment and automobiles. It can be used as a molded product in the field.

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